CN103272491A - Preparation method for in situ self-assembled organic/inorganic hybrid membrane based on coordination - Google Patents
Preparation method for in situ self-assembled organic/inorganic hybrid membrane based on coordination Download PDFInfo
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Abstract
The invention provides a preparation method for an in situ self-assembled organic/inorganic hybrid membrane based on coordination, and belongs to the technical field of membrane separation. The method provided by the invention comprises the following steps: preprocessing the organic porous membrane and enabling the surface of which to be charged; preparing membrane casting solution by dissolving metal ion, organic ligand and polymer in a solution, and carrying out standing of the membrane casting solution for deaeration; conducting dynamic filtering or static deposition of the membrane casting solution on the surface of the organic porous membrane in an alternating manner for a period of time, so as to enable the metal ion and the organic ligand to generate hybrid particle on the surface of the membrane through the layer upon layer self-assembly method in the presence of polyelectrolyte, and forming an ultra-thin separation layer which is uniform in dispersity, high in loading capacity, and can realize molecular hybridization. The invention provides a novel preparation method for the organic/inorganic hybrid membrane, and nanofiltration membrane prepared by the method is provided with the advantages of high reject rate, big flux and the like, and the method can be widely used in the filed of water processing.
Description
Technical field
The present invention relates to a kind of preparation method of the original position self assembly hybrid film based on coordination, be used for removing of dyestuff, belong to the membrane separation technique field.
Background technology
Film separates as a kind of new separation technology, has simple to operate, characteristics such as energy consumption is low, good separating effect, non-secondary pollution, receives increasing concern.The character of membrane material is one of key factor that influences membrane separating effect, and the hybrid film combines organic polymer and inorganic material, and performance advantage separately is with a wide range of applications in the composite membrane preparation.There are some researches show, organic film of the inorganic nano-particle that mixed separating effect and stable aspect in various degree raising is arranged.The preparation method of the hybrid film that generally adopts is blending method at present, and this method directly is entrained in inorganic nano-particle in the solution of organic polymer, prepares film forming then.The even aggregation phenomenon of nano particle skewness easily takes place in the hybridized film of this method preparation, thereby causes the instability of hybridized film performance, and because organic and inorganic mutually consistency problem can cause the loss of inorganic nano-particle.The invention provides a kind of original position self-assembling method of novel hybrid film, can be in the preparation process of composite membrane in-situ growth nano-particle, preferably resolve the shortcoming of inorganic nano-particle bad dispersibility, and utilize electrostatic interaction and coordination between organic polymer and the inorganic nano-particle to improve organic phase and inorganic alternate compatibility, thereby improved separating property and the stability of hybridized film, had important scientific value and application prospect.
Summary of the invention
The method that the purpose of this invention is to provide a kind of original position self assembly organic/inorganic nano hybridized film.Metal ion and organic ligand are doped in the polyelectrolyte, and the method by self assembly layer by layer generates hybrid particle on the surface of basement membrane, prepares that a kind of dispersiveness is even, load capacity is high, can realize the hybrid film of molecule aspect hydridization.Characteristics such as the NF membrane that adopts this kind method to prepare has the rejection height, and flux is big can be widely used in water treatment field.
This method may further comprise the steps:
(1) polyelectrolyte, metal ion and organic ligand are dissolved in respectively in the solvent, are mixed with polyelectrolyte solution, metal ion solution and organic ligand solution, standing and defoaming;
(2) organic porous films is carried out preliminary treatment (as plasma treatment, hydrolysis process, radiation treatment etc.), make its surperficial bear electricity in order to react with metal ion, or lotus positive electricity is in order to react with organic ligand;
(3) metal ion solution and polyelectrolyte solution are mixed formation metal ion-polyelectrolyte mixed liquor; Organic ligand solution and polyelectrolyte solution mix formation organic ligand-polyelectrolyte mixed liquor;
(4) with step (3) mixed liquor 0～220 ℃ temperature and 0～1.0MPa pressure or-0.02～-suction function of 0.09MPa under at organic porous films surface static deposition or dynamic filtration 5s～36000s, metal ion and polyelectrolyte are combined in the skin and hole of organic porous films of bear electricity, machine part and polyelectrolyte are combined in the skin and hole of organic porous films of lotus positive electricity;
(5) step (4) organic porous films is clean with rinsed with deionized water, in 30～100 ℃ of scopes, dry;
(6) with step (3) organic ligand-polyelectrolyte mixed liquor 0～220 ℃ temperature and 0～1.0MPa pressure or-0.02～-suction function of 0.09MPa under, be combined with organic porous films surface static deposition or the dynamic filtration 5s～36000s of metal ion and polyelectrolyte, or with step (3) metal ion-polyelectrolyte mixed liquor 0～220 ℃ temperature and 0～1.0MPa pressure or-0.02～-suction function of 0.09MPa under, be combined with organic porous films surface static deposition or the dynamic filtration 5s～36000s of organic ligand and polyelectrolyte, make organic ligand and metal ion generation coordination generate organometallic skeletal compound (MOF) crystal, polyelectrolyte also is combined in the film surface under the promotion of electrostatic force and chemical action power simultaneously, with the uniform separating layer of the common formation of MOF crystal;
(7) organic porous films is clean with rinsed with deionized water, in 30～100 ℃ of scopes, dry or dry;
(8) repeat (6)～(7) step 0～100 times, realize the assembling of multilayer complex films at organic porous films.
The described metal ion of step (1) is for can synthesize the metal ion of MOF (as Cu
2+, Zn
2+, Al
3+Deng); Described organic ligand is for synthesizing the organic matter (as pyridine, imidazoles, trimesic acid etc.) of MOF; Described polyelectrolyte is to produce (as kayexalate (PSS), polymine (PEI) etc.) such as the polymer of active force, the surfactants of modification with metal ion or organic ligand.Described solvent can be water, methyl alcohol, ethanol, propyl alcohol, butanols etc.When step (3) configuration metal ion-polyelectrolyte mixed liquor and organic ligand-polyelectrolyte mixed liquor, the mol ratio of preferred polyelectrolyte and metal ion or organic coordination compound is 100:1～1:100, perhaps in above-mentioned assembling process in metal ion or the organic coordination compound one of with the mol ratio of polyelectrolyte be 0.
In the method for the invention, described organic porous films is NF membrane, milipore filter or micro-filtration membrane, the membrane material of described organic porous films is organic polymers such as polyacrylonitrile, polysulfones, polyether sulfone, Kynoar, the kit form of described organic porous films is tubular type, doughnut formula, flat or rolling, and the membrane aperture of described organic porous films is between 1 nanometer to 100 micron.
The present invention is based on the MOF material of coordination and the original position self-assembling method of polyelectrolyte hydridization, namely at first preliminary treatment is carried out in substrate, make its surface have can with the functional group of organic ligand or metal ion generation coordination, alternately assemble required metal ion or the organic ligand of MOF material growth then in the presence of polymer, repeated multiple times just can form ultra-thin nanoscale hybrid film.
The principle of technical solution of the present invention is: metal ion or organic ligand and polyelectrolyte with functional group produce coordination, hydridization is in the segment of polymer, metal ion and organic ligand original position under the driving of coordination generates the MOF material simultaneously, thereby makes a kind of organic/inorganic composite film in molecule aspect hydridization.Because the method realized the hydridization of molecule aspect, thus have hybrid particle load capacity height, be evenly distributed, the interface in conjunction with closely, be difficult for producing advantage such as defective.
Compared with prior art, the present invention has following advantage:
One, can make film be applied to different separation systems by changing the multiple different MOF material of kind type load of metal ion and organic ligand;
Two, because hydridization can be controlled in the molecule aspect, so increased the specific area of film, improved the performance of film, especially aspect flux;
Three, the diffusion barrier of assembling is having significant raising aspect acid-proof alkaline, solvent resistance and the stain resistance.
Below in conjunction with description of drawings and the specific embodiment the present invention is described in further detail.
Description of drawings
Fig. 1 is the film surface scan electronic microscope photos of embodiment 2.
Fig. 2 is the film surface scan electronic microscope photos of embodiment 3.
Fig. 3 is the film surface scan electronic microscope photos of embodiment 4.
Fig. 4 is the film surface scan electronic microscope photos of embodiment 5.
The specific embodiment
Below in conjunction with the drawings and specific embodiments the present invention is described in detail.
Embodiment 1
The employing basement membrane is polyacrylonitrile (PAN) material, flat milipore filter, and molecular cut off 20,000, membrane area are 20cm
2, used polyelectrolyte is kayexalate (PSS, molecular weight are 1,000,000); Metal ion is zinc nitrate hexahydrate (Zn (NO
3) 6H
2O, molecular weight are 297.49); Organic ligand is glyoxal ethyline (C
4H
6N
2, molecular weight is 82.10).The solvent of zinc nitrate hexahydrate and glyoxal ethyline is methyl alcohol, and the solvent of kayexalate is water.
Assembling condition and method:
(1) with deionized water kayexalate is made into the solution 500ml of 3wt%, standing and defoaming; With methyl alcohol zinc nitrate hexahydrate is made into the solution 500ml of 0.05mol/L, standing and defoaming; With methyl alcohol glyoxal ethyline is made into the solution 500ml of 0.4mol/L, standing and defoaming;
(2) for making polyacrylonitrile stayed surface band carboxyl, adopt conventional hydrolyzed modified technology, at first when temperature is 65 ℃, polyacrylonitrile ultrafiltration film is immersed 30min in the 2mol/L NaOH solution, make its surperficial itrile group be converted into carboxyl;
(3) film is immersed in the deionized water rinsing face and oven dry;
(4) film is immersed in the zinc nitrate hexahydrate methanol solution of 0.05mol/L, 65 ℃ of heating 60min make zinc ion be assembled in the film surface;
(5) film is immersed in the deionized water rinsing face and oven dry;
(6) 3wt%PSS solution is mixed standing and defoaming with 0.4mol/L2-methylimidazole solution with the ratio of 1:1;
(7) under the suction function of-0.09Mpa, filter mixed liquor 30min, make the Zn ion produce coordination with glyoxal ethyline and PSS respectively, form hybridized film;
(8) film is immersed in the deionized water rinsing face and oven dry; Can form the compound number of plies and be 1 layer nanoscale molecular hydridization NF membrane.
The nanoscale molecular hybridized film of above-mentioned assembling is removed the dyestuff performance test in nanofiltration device, test condition is: material liquid is methyl blue (M=799.8) solution of 0.1g/L, tests under the room temperature, and pressure is 0.5MPa.
Recording hybridized film to the performance that removes of methyl blue is: percolate flux 358.615kgm
-2H
-1MPa
-1, the methyl blue removal efficiency is 92.743%.
Embodiment 2
The employing basement membrane is polyacrylonitrile (PAN) material, flat milipore filter, and molecular cut off 20,000, membrane area are 20cm
2, used polyelectrolyte is kayexalate (PSS, molecular weight are 1,000,000); Metal ion is zinc nitrate hexahydrate (Zn (NO
3) 6H
2O, molecular weight are 297.49); Organic ligand is glyoxal ethyline (C
4H
6N
2, molecular weight is 82.10).The solvent of zinc nitrate hexahydrate and glyoxal ethyline is methyl alcohol, and the solvent of kayexalate is water.
Assembling condition and method:
(1) with deionized water kayexalate is made into the solution 500ml of 0.3wt%, standing and defoaming; With methyl alcohol zinc nitrate hexahydrate is made into the solution 500ml of 0.05mol/L, standing and defoaming; With methyl alcohol glyoxal ethyline is made into the solution 500ml of 0.4mol/L, standing and defoaming.
(2) for making polyacrylonitrile stayed surface band carboxyl, adopt conventional hydrolyzed modified technology, at first when temperature is 65 ℃, polyacrylonitrile ultrafiltration film is immersed 30min in the 2mol/L NaOH solution, make its surperficial itrile group be converted into carboxyl;
(3) film is immersed in the deionized water rinsing face and oven dry;
(4) film is immersed in the zinc nitrate hexahydrate methanol solution of 0.05mol/L, 65 ℃ of heating 60min make zinc ion be assembled in the film surface;
(5) film is immersed in the deionized water rinsing face and oven dry;
(6) 0.3wt%PSS solution is mixed standing and defoaming with 0.4mol/L2-methylimidazole solution with the ratio of 1:1;
(7) under the suction function of-0.09Mpa, filter mixed liquor 30min, make the Zn ion produce coordination with glyoxal ethyline and PSS respectively, form hybridized film;
(8) film is immersed in the deionized water rinsing face and oven dry;
(9) repeat (4)-(8) step 1 time, can form the compound number of plies and be 2 layers nanoscale molecular hydridization NF membrane.
The nanoscale molecular hybridized film of above-mentioned assembling is removed the dyestuff performance test in nanofiltration device, test condition is: material liquid is methyl blue (M=799.8) solution of 0.1g/L, tests under the room temperature, and pressure is 0.5MPa.
Recording hybridized film to the performance that removes of methyl blue is: percolate flux 271.775kgm
-2H
-1MPa
-1, the methyl blue removal efficiency is 99.0%.
Embodiment 3
The employing basement membrane is polyacrylonitrile (PAN) material, flat milipore filter, and molecular cut off 20,000, membrane area are 20cm
2, used polyelectrolyte is kayexalate (PSS, molecular weight are 1,000,000); Metal ion is zinc nitrate hexahydrate (Zn (NO
3) 6H
2O, molecular weight are 297.49); Organic ligand is glyoxal ethyline (C
4H
6N
2, molecular weight is 82.10).The solvent of zinc nitrate hexahydrate and glyoxal ethyline is methyl alcohol, and the solvent of kayexalate is water.
Assembling condition and method:
(1) with deionized water kayexalate is made into the solution 500ml of 0.3wt%, standing and defoaming; With methyl alcohol zinc nitrate hexahydrate is made into the solution 500ml of 0.5mol/L, standing and defoaming; With methyl alcohol glyoxal ethyline is made into the solution 500ml of 4mol/L, standing and defoaming;
(2) for making polyacrylonitrile stayed surface band carboxyl, adopt conventional hydrolyzed modified technology, at first when temperature is 65 ℃, polyacrylonitrile ultrafiltration film is immersed 30min in the 2mol/L NaOH solution, make its surperficial itrile group be converted into carboxyl;
(3) film is immersed in the deionized water rinsing face and oven dry;
(4) film is immersed in the zinc nitrate hexahydrate methanol solution of 0.5mol/L, 65 ℃ of heating 60min make zinc ion be assembled in the film surface;
(5) film is immersed in the deionized water rinsing face and oven dry;
(6) 0.3wt%PSS solution is mixed standing and defoaming with 4mol/L2-methylimidazole solution with the ratio of 1:1;
(7) under the suction function of-0.09Mpa, filter mixed liquor 30min, make the Zn ion produce coordination with glyoxal ethyline and PSS respectively, form hybridized film;
(8) film is immersed in the deionized water rinsing face and oven dry;
(9) repeat (4)-(8) step 1 time, can form the compound number of plies and be 2 layers nanoscale molecular hydridization NF membrane.
The nanoscale molecular hybridized film of above-mentioned assembling is removed the dyestuff performance test in nanofiltration device, test condition is: material liquid is methyl blue (M=799.8) solution of 0.1g/L, tests under the room temperature, and pressure is 0.5MPa.
Recording hybridized film to the performance that removes of methyl blue is: percolate flux 52.94kgm
-2H
-1MPa
-1, the methyl blue removal efficiency is 99.84%.
Embodiment 4
The employing basement membrane is polyacrylonitrile (PAN) material, flat milipore filter, and molecular cut off 20,000, membrane area are 20cm
2, used polyelectrolyte is kayexalate (PSS, molecular weight are 1,000,000); Metal ion is zinc nitrate hexahydrate (Zn (NO
3) 6H
2O, molecular weight are 297.49); Organic ligand is glyoxal ethyline (C
4H
6N
2, molecular weight is 82.10).The solvent of zinc nitrate hexahydrate and glyoxal ethyline is methyl alcohol, and the solvent of kayexalate is water.
Assembling condition and method:
(1) with deionized water kayexalate is made into the solution 500ml of 0.3wt%, standing and defoaming; With methyl alcohol zinc nitrate hexahydrate is made into the solution 500ml of 0.05mol/L, standing and defoaming; With methyl alcohol glyoxal ethyline is made into the solution 500ml of 0.4mol/L, standing and defoaming;
(2) for making polyacrylonitrile stayed surface band carboxyl, adopt conventional hydrolyzed modified technology, at first when temperature is 65 ℃, polyacrylonitrile ultrafiltration film is immersed 30min in the 2mol/L NaOH solution, make its surperficial itrile group be converted into carboxyl;
(3) film is immersed in the deionized water rinsing face and oven dry;
(4) film is immersed in the zinc nitrate hexahydrate methanol solution of 0.05mol/L, 65 ℃ of heating 60min make zinc ion be assembled in the film surface;
(5) film is immersed in the deionized water rinsing face and oven dry;
(6) 0.3wt%PSS solution is mixed standing and defoaming with 0.4mol/L2-methylimidazole solution with the ratio of 1:1;
(7) under the suction function of-0.09Mpa, filter mixed liquor 30min, make the Zn ion produce coordination with glyoxal ethyline and PSS respectively, form hybridized film;
(8) film is immersed in the deionized water rinsing face and oven dry;
(9) repeat (4)-(8) step 2 time, can form the compound number of plies and be 3 layers nanoscale molecular hydridization NF membrane.
The nanoscale molecular hybridized film of above-mentioned assembling is removed the dyestuff performance test in nanofiltration device, test condition is: material liquid is methyl blue (M=799.8) solution of 0.1g/L, tests under the room temperature, and pressure is 0.5MPa.
Recording hybridized film to the performance that removes of methyl blue is: percolate flux 113.465kgm
-2H
-1MPa
-1, the methyl blue removal efficiency is 99.97%.
Embodiment 5
The employing basement membrane is polyacrylonitrile (PAN) material, flat milipore filter, and molecular cut off 20,000, membrane area are 20cm
2, used polyelectrolyte is kayexalate (PSS, molecular weight are 1,000,000); Metal ion is zinc nitrate hexahydrate (Zn (NO
3) 6H
2O, molecular weight are 297.49); Organic ligand is glyoxal ethyline (C
4H
6N
2, molecular weight is 82.10).The solvent of zinc nitrate hexahydrate and glyoxal ethyline is methyl alcohol, and the solvent of kayexalate is water.
Assembling condition and method:
(1) with deionized water kayexalate is made into the solution 500ml of 0.3wt%, standing and defoaming; With methyl alcohol zinc nitrate hexahydrate is made into the solution 500ml of 0.05mol/L, standing and defoaming; With methyl alcohol glyoxal ethyline is made into the solution 500ml of 0.4mol/L, standing and defoaming;
(2) for making polyacrylonitrile stayed surface band carboxyl, adopt conventional hydrolyzed modified technology, at first when temperature is 65 ℃, polyacrylonitrile ultrafiltration film is immersed 30min in the 2mol/L NaOH solution, make its surperficial itrile group be converted into carboxyl;
(3) film is immersed in the deionized water rinsing face and oven dry;
(4) film is immersed in the zinc nitrate hexahydrate methanol solution of 0.05mol/L, 65 ℃ of heating 60min make zinc ion be assembled in the film surface;
(5) film is immersed in the deionized water rinsing face and oven dry;
(6) 0.3wt%PSS solution is mixed standing and defoaming with 0.4mol/L2-methylimidazole solution with the ratio of 1:1;
(7) under the suction function of-0.09Mpa, filter mixed liquor 30min, make the Zn ion produce coordination with glyoxal ethyline and PSS respectively, form hybridized film;
(8) film is immersed in the deionized water rinsing face and oven dry;
(9) repeat (4)-(8) step 5 time, can form the compound number of plies and be 6 layers nanoscale molecular hydridization NF membrane.
The nanoscale molecular hybridized film of above-mentioned assembling is removed the dyestuff performance test in nanofiltration device, test condition is: material liquid is methyl blue (M=799.8) solution of 0.1g/L, tests under the room temperature, and pressure is 0.5MPa.
Recording hybridized film to the performance that removes of methyl blue is: percolate flux 34.53kgm
-2H
-1MPa
-1, the methyl blue removal efficiency is 100%.
Embodiment 6
The employing basement membrane is polyacrylonitrile (PAN) material, flat milipore filter, and molecular cut off 20,000, membrane area are 20cm
2, used polyelectrolyte is polymine (PEI, molecular weight are 60000); Metal ion is Gerhardite (Cu (NO
3) 3H
2O, molecular weight are 241.6); Organic ligand is trimesic acid (H
3BTC, molecular weight are 210.14).The solvent of Gerhardite and trimesic acid is methyl alcohol, and the solvent of polymine is water.
Assembling condition and method:
(1) with deionized water polymine is made into the solution 500ml of 2.5wt%, standing and defoaming; With methyl alcohol Gerhardite is made into the solution 500ml of 0.0025mol/L, standing and defoaming; With methyl alcohol trimesic acid is made into the solution 500ml of 0.0025mol/L, standing and defoaming;
(2) for making polyacrylonitrile stayed surface band carboxyl, adopt conventional hydrolyzed modified technology, at first when temperature is 65 ℃, polyacrylonitrile ultrafiltration film is immersed 30min in the 2mol/L NaOH solution, make its surperficial itrile group be converted into carboxyl;
(3) film is immersed in the deionized water rinsing face and oven dry;
(4) 2.5wt%PEI solution is mixed standing and defoaming with the 0.0025mol/L Gerhardite with the ratio of 1:24;
(5) under the suction function of-0.09Mpa, filter mixed liquor 30min, make Cu
2+Be assembled in the film surface with PEI;
(6) film is immersed in the deionized water rinsing face and oven dry;
(7) film is immersed in the trimesic acid methanol solution of 0.0025mol/L, 65 ℃ of heating 60min make BTC
-Respectively with Cu
2+Produce coordination with PEI, form hybridized film;
(8) film is immersed in the deionized water rinsing face and oven dry;
(9) repeat (4)-(8) step 1 time, can form the compound number of plies and be 2 layers nanoscale molecular hydridization NF membrane.
The nanoscale molecular hybridized film of above-mentioned assembling is removed the dyestuff performance test in nanofiltration device, test condition is: material liquid is methyl blue (M=799.8) solution of 0.1g/L, tests under the room temperature, and pressure is 0.5MPa.
Recording hybridized film to the performance that removes of methyl blue is: percolate flux 41.58kgm
-2H
-1MPa
-1, the methyl blue removal efficiency is 99.1%.
Claims (7)
1. the preparation method based on the original position self assembly hybrid film of coordination is characterized in that, may further comprise the steps:
(1) polyelectrolyte, metal ion and organic ligand are dissolved in respectively in the solvent, are mixed with polyelectrolyte solution, metal ion solution and organic ligand solution, standing and defoaming;
(2) organic porous films is carried out preliminary treatment, make its surperficial bear electricity in order to react with metal ion, or lotus positive electricity is in order to react with organic ligand;
(3) metal ion solution and polyelectrolyte solution are mixed formation metal ion-polyelectrolyte mixed liquor; Organic ligand solution and polyelectrolyte solution mix formation organic ligand-polyelectrolyte mixed liquor;
(4) with step (3) mixed liquor 0～220 ℃ temperature and 0～1.0MPa pressure or-0.02～-suction function of 0.09MPa under at organic porous films surface static deposition or dynamic filtration 5s～36000s, metal ion and polyelectrolyte are combined in the skin and hole of organic porous films of bear electricity, machine part and polyelectrolyte are combined in the skin and hole of organic porous films of lotus positive electricity;
(5) step (4) organic porous films is clean with rinsed with deionized water, in 30～100 ℃ of scopes, dry;
(6) with step (3) organic ligand-polyelectrolyte mixed liquor 0～220 ℃ temperature and 0～1.0MPa pressure or-0.02～-suction function of 0.09MPa under, be combined with organic porous films surface static deposition or the dynamic filtration 5s～36000s of metal ion and polyelectrolyte, or with step (3) metal ion-polyelectrolyte mixed liquor 0～220 ℃ temperature and 0～1.0MPa pressure or-0.02～-suction function of 0.09MPa under, be combined with organic porous films surface static deposition or the dynamic filtration 5s～36000s of organic ligand and polyelectrolyte, make organic ligand and metal ion generation coordination generate organometallic skeletal compound (MOF) crystal, polyelectrolyte also is combined in the film surface under the promotion of electrostatic force and chemical action power simultaneously, with the uniform separating layer of the common formation of MOF crystal;
(7) organic porous films is clean with rinsed with deionized water, in 30～100 ℃ of scopes, dry or dry;
(8) repeat (6)～(7) step 0～100 times, realize the assembling of multilayer complex films at organic porous films.
2. according to the method for claim 1, it is characterized in that, when step (3) configuration metal ion-polyelectrolyte mixed liquor and organic ligand-polyelectrolyte mixed liquor, the mol ratio of preferable alloy ion or organic coordination compound and polyelectrolyte is 100:1～1:100, perhaps in above-mentioned assembling process in metal ion or the organic coordination compound one of with the mol ratio of polyelectrolyte be 0.
3. according to the method for claim 1, it is characterized in that described metal ion is for synthesizing the metal ion of MOF; Described organic ligand is for synthesizing the organic matter of MOF; Described polyelectrolyte is to produce the polymer of active force, the surfactant of modification with metal ion or organic ligand.
4. according to the method for claim 1, it is characterized in that described metal ion is Cu
2+, Zn
2+, Al
3+Described organic ligand is as pyridine, imidazoles, trimesic acid; Described polyelectrolyte is kayexalate (PSS) or polymine (PEI).
5. according to the method for claim 1, it is characterized in that described solvent is water, methyl alcohol, ethanol, propyl alcohol or butanols.
6. according to the method for claim 1, it is characterized in that, described organic porous films is NF membrane, milipore filter or micro-filtration membrane, the membrane material of described organic porous films is organic polymers such as polyacrylonitrile, polysulfones, polyether sulfone, Kynoar, the kit form of described organic porous films is tubular type, doughnut formula, flat or rolling, and the membrane aperture of described organic porous films is between 1 nanometer to 100 micron.
7. according to the prepared hybrid film of the described arbitrary method of claim 1-6.
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